This invention relates to the use of novel methyl substituted pinyl oxopentenes defined according to the generic structure: ##STR1## and the generic structure: ##STR2## wherein Z represents methylidene defined according to the structure: ##STR3## ethylidene defined according to the structure: ##STR4## or ethylenyl defined according to the structure: ##STR5## wherein one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents no bond; wherein n is 0 or 1 and m is 0 or 1 with the sum of n+m being equal to 1; wherein X represents carbinol having the structure: ##STR6## or ketone having the structure: ##STR7## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl; wherein one of the lines: EQU + + + +
represents a carbon-carbon single bond and the other of the lines: EQU + + + +
represents a carbon-carbon single bond or a carbon-carbon double bond; wherein one of the lines: EQU /+/+/+/+/+/
represents a carbon-carbon single bond and the other of the lines: EQU /+/+/+/+/+/
represents a carbon-carbon single bond or a carbon-carbon double bond; with the provisos that:
(i) when R.sub.3 and R.sub.4 are each hydrogen, the dashed line at the 7-5 position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR8## or ethylenyl having the structure: ##STR9## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR10## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and PA1 (iv) when R.sub.4 is methyl, then R.sub.3 is hydrogen, n is 0 and m is 1; and wherein one of the lines: PA1 (i) when R.sub.3 and R.sub.4 are each hydrogen, the dashed line at the 7-5 position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR27## or ethylenyl having the structure: ##STR28## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR29## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and PA1 (iv) when R.sub.4 is methyl, then R.sub.3 is hydrogen, n is 0 and m is 1 wherein one of the lines: PA1 (ii) when one of R.sub.3 or R.sub.4 is methyl and the other of R.sub.3 or R.sub.4 is hydrogen, then p and q are both 0; PA1 (iii) when R.sub.3 is methyl, then R.sub.4 is hydrogen and the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and m is 0; n is 1 and q is 0; PA1 (iv) when R.sub.4 is methyl and R.sub.3 is hydrogen, then n is 0 and m is 1 and p is 0 and one of the dashed lines at the 7-5 position or the 7-4 position is a carbon-carbon single bond; PA1 p-hydroxybenzylacetone; PA1 geraniol; PA1 cassia oil; PA1 acetaldehyde; PA1 maltol; PA1 ethyl methyl phenyl glycidate; PA1 benzyl acetate; PA1 dimethyl sulfide; PA1 eugenol; PA1 vanillin; PA1 caryophyllene; PA1 guaiacol; PA1 ethyl pelargonate; PA1 cinnamaldehyde; PA1 methyl anthranilate; PA1 5-methyl furfural; PA1 isoamyl acetate; PA1 isobutyl acetate; PA1 cuminaldehyde; PA1 alpha ionone; PA1 ethyl butyrate; PA1 methyl cinnamate; PA1 acetic acid; PA1 gamma-undecalactone; PA1 naphthyl ethyl ether; PA1 diacetyl; PA1 furfural; PA1 ethyl acetate; PA1 anethole; PA1 2,3-dimethyl pyrazine; PA1 2-ethyl-3-methyl pyrazine; PA1 3-phenyl-4-pentenal; PA1 2-phenyl-2-hexanal; PA1 2-phenyl-2-pentenal; PA1 2-phenyl-4-pentenal diethyl acetal; PA1 beta-damascone (1-crotonyl-2,6,6-trimethyl-cyclohex-1-ene); PA1 beta-damascenone (1crotonyl-2,6,6-trimethyl-cyclohexa1,3-diene); PA1 beta-cyclohomocitral (2,6,6,-trimethylcyclohex-1-ene carboxaldehyde); PA1 isoamyl butyrate; PA1 cis-3-hexanol-1; PA1 2-methyl-2-pentenoic acid; PA1 elemecine (4-allyl-1,2,6-trimethoxybenzene); PA1 isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and PA1 2-(4-hydroxy-4-methylpentyl)norbornadiene. PA1 (i) 4-methyl-3-cyclohexene-1-carboxylic acid having the structure: ##STR58## taken alone or taken further together with other compounds which yield sweaty, animal, leathery notes defined according to genera having the structures: PA1 (ii) ##STR59## wherein R represents t-butyl or t-amyl as more specifically described in U.S. Pat. No. 3,702,343 issued on Nov. 7, 1972, the disclosure for which is incorporated by reference herein. PA1 (i) Synthetic Materials: PA1 (ii) Natural Oils: PA1 (i) when R.sub.3 and R.sub.4 are each hydrogen, the dashed line at the 7-5 position is a carbon-carbon single bond; n=0 and m is 1; Z represents ethylidene having the structure: ##STR73## or ethylenyl having the structure: ##STR74## (ii) when one of R.sub.3 or R.sub.4 is methyl, then either the dashed line at the 7-5 position or the dashed line at the 7-4 position is a carbon-carbon single bond; and Z represents methylidene defined according to the structure: ##STR75## (iii) when R.sub.3 is methyl, then n is 1 and m is 0 and R.sub.4 is hydrogen; and PA1 (iv) when R.sub.4 is methyl, then R.sub.3 is hydrogen, n is 0 and m is 1
represents a carbon-carbon double bond and the other of the line:
represents a carbon-carbon single bond; and uses thereof in augmenting or enhancing the aroma or taste of consumable materials.
Materials which can provide sandalwood-like, urine-like and musky aromas with floral and muguet undertones are desirable and are known in the art of perfumery. Many of the natural materials which provide such fragrances and such desired nuances to perfumery compositions and perfumed articles are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
By the same token, materials which can provide ionone-like, raspberry-like, oriental, floral, violet, musky and fruity aromas with sweet, ionone-like, raspberry, fruity and lactonic tastes are desirable and are well known in the art of flavoring for foodstuffs, toothpastes, chewing gums, medicinal products and chewing tobaccos. Many of the natural materials which provide such flavor notes and contribute such desired nuances to flavor and to compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
By the same token, materials which can provide sweet, woody, oriental, ionone-like, sandalwood-like, patchouli-like and cigar box-like aroma and taste nuances to smoking tobacco or smoking tobacco article components both prior to smoking and on smoking in the main stream and in the side stream are highly desirable and are well known in the art of flavoring for smoking tobacco and components for smoking tobacco articles such as filters and wrappers. Many of the natural materials which provide such aroma and taste nuances and contribute the desired nuances to tobacco flavoring compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
Artificial flavoring agents for foodstuffs have received increasing attention in recent years. For many years such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in quality, type and treatment of the raw materials. Such variations can be reflected in the end products and result in unfavorable flavor characteristics in said end product, for example, blackberry, peach and tropical fruit flavored foodstuffs. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and the like are apt to be stored prior to use.
The fundamental problem in creating artificial flavor agents if that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods, medicinal products, chewing gums and toothpastes is not completely known. This is particularly noticeable in products having blackberry, peach and tropical fruit characteristics particularly.
Even more desirable are products which can serve to substitute for difficult to obtain natural perfumery oils and, at the same time, substitute for natural flavoring ingredients in foodstuffs, chewing gums, medicinal products, toothpastes, chewing tobaccos, and smoking tobaccos.
Pinyl pentenol derivatives are known in the art for having sandalwood aromas. Thus, the compound having the structure: ##STR11## is shown to be prepared according to German Offenlegungsschrift No. 2708048 which, generically, discloses synthesis of compounds defined according to the structure: ##STR12## wherein R.sub.1 and R.sub.2 taken together can represent dimethyl bicyclo[3.1.1] heptyl; R.sub.3 represents alkyl; R.sub.4 represents alkyl and Y represents a divalent aliphatic group with at least four carbon atoms. Thus, German Offenlegungsschrift No. 2708048 discloses the reaction sequence, starting with pinene and ending up with a tertiary pentenol thusly: ##STR13## None of the chemicals produced using the process of our invention are tertiary alcohols and the chemicals produced according to the process of our invention are not considered to be similar from a chemical and organoleptic standpoint to the compounds of German Offenlegungsschrift No. 2708048.
German Offenlegungsschrift No. 2708048 is abstracted at Volume 87, 1977, 184084f of Chemical Abstracts.
Himmele and Siegel, Tetrahedron Letters No. 12, pages 907-910, 1976 in the paper entitled "Hydroformylierung Von Alpha-Pinen" discloses the reaction sequence, starting with alpha pinen first going to a carboxaldehyde according to the reaction sequences: ##STR14##
German Offenlegungsschrift No. 2849742 abstracted in Chem. Abstracts 1981, No. 186613a (Hagen and Bruns) published May 22, 1980 discloses the hydroformylation of monocyclic or bicyclic terpenes with at least one double bond in the presence of a rhodium complex containing triphenylphosphine at 70.degree.-160.degree. C. at 100-400 bar to give the corresponding terpenecarboxaldehydes and alleges that these terpenecarboxaldehydes are useful as perfume ingredients. Specifically, Hagen and Bruns state that 3,3-dimethyl-2-norobornane acetaldehyde and 10-formylpinane are prepared from camphene or beta-pinene. Furthermore, U.S. Pat. No. 3,716,498 issued on Feb. 13, 1973 indicates that such compounds as 6,6-dimethyl-bicyclo[3.1.1]hept-2-ene-2-propionaldehyde are capable of augmenting or enhancing the aroma of perfume compositions, for example, in order to give "fresh air qualities" to Foin Coupe cologne blends. Cosmetic Technology, April 1981 at page 18 states that Sandalore.RTM. manufactured by the Givaudan Corporation of Clifton, New Jersey is a useful sandalwood fragrance and has approximately twice the amount of odor intensity of sandalwood oil. Sandalore.RTM. is a mixture of compounds defined according to the structures: ##STR15##
Application for U.S. Pat. Ser. No. 391,592 filed on June 24, 1982, now U.S. Pat. No. 4,390,434 issued on June 28, 1983 describes the compound, 4-methyl-3-cyclohexene-1-carboxylic acid having the structure: ##STR16## and uses thereof in augmenting or enhancing the aroma of perfume compositions, perfumed articles and colognes, particularly as a replacement for cumin oil and/or cumin aldehyde and the combination of this compound with compounds which yield sweaty, animal, leathery notes defined according to the genera having the structures: ##STR17## wherein R represents t-butyl or t-amyl as more particularly described in U.S. Pat. No. 3,702,343 issued on Nov. 7, 1972. The use of the mixtures of compounds disclosed in application for U.S. Pat. Ser. No. 391,592 filed on June 24, 1982, now U.S. Pat. No. 4,390,434 issued on June 28, 1983 in combination with the methyl substituted pinyl oxopentenes of our invention is also contemplated within the scope of our invention.
Nothing in the prior art, however, sets forth the products, processes or unique uses of the compositions of matter of our invention. Indeed, the compositions of matter of our invention either as mixtures or products per se, have unexpected, unobvious and advantageous properties over remotely similar compounds set forth in the prior art, for example, the compounds of the German Offenlegungsschrift No. 2708048.
United Kingdom Specification No. 1,471,856 published on Apr. 27, 1977 discloses the reaction sequence: ##STR18## wherein K' represents the catalyst having the structure: ##STR19##
The products produced according to U.K. Specification No. 1,471,856 are structurally dissimilar from the products of the instant invention.